JP2000129087A - Epoxy resin composition, prepreg, resin-coated metallic foil and laminate - Google Patents
Epoxy resin composition, prepreg, resin-coated metallic foil and laminateInfo
- Publication number
- JP2000129087A JP2000129087A JP30506898A JP30506898A JP2000129087A JP 2000129087 A JP2000129087 A JP 2000129087A JP 30506898 A JP30506898 A JP 30506898A JP 30506898 A JP30506898 A JP 30506898A JP 2000129087 A JP2000129087 A JP 2000129087A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- epoxy resin
- epoxy
- prepreg
- copper foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、プリント配線板な
どの製造に用いられるエポキシ樹脂組成物、プリプレ
グ、樹脂付き金属箔及び積層板に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, a prepreg, a metal foil with a resin, and a laminate used for manufacturing a printed wiring board and the like.
【０００２】[0002]
【従来の技術】電気機器、電子機器などに使用されるプ
リント配線板は、熱硬化性樹脂ワニスをガラスクロスな
どの基材に含浸してプリプレグを調製し、このプリプレ
グを所要枚数重ねると共にその上下に銅箔等の金属箔を
配置し、これを加熱加圧して積層成形することによって
金属箔張り積層板を作製し、表面の金属箔をプリント配
線加工して回路形成することによって、製造されてい
る。そしてこのプリント配線板を内層回路板とし、この
プリント配線板に所要枚数のプリプレグを重ねると共に
その外側に金属箔を配置し、これを加熱加圧して積層成
形した後に、外層の金属箔をプリント配線加工して回路
形成したりスルホール加工したりすることによって、多
層プリント配線板を製造することができる。2. Description of the Related Art A printed wiring board used for electric equipment and electronic equipment is prepared by impregnating a base material such as a glass cloth with a thermosetting resin varnish to prepare a prepreg. A metal foil such as a copper foil is placed on a metal foil-clad laminate by heating and pressurizing and laminating the metal foil to produce a metal foil-clad laminate. I have. The printed wiring board is used as an inner layer circuit board. A required number of prepregs are stacked on the printed wiring board, and a metal foil is arranged on the outside of the printed wiring board. A multilayer printed wiring board can be manufactured by processing to form a circuit or through-hole processing.
【０００３】ここで、上記のプリプレグとしては、一般
に、熱硬化性樹脂としてエポキシ樹脂を用い、ガラスク
ロスなどの基材にエポキシ樹脂ワニスを含浸して加熱乾
燥することによって半硬化状態（Ｂ−ステージ）にした
ものが使用されている。[0003] Here, the prepreg is generally made of a semi-cured state (B-stage) by using an epoxy resin as a thermosetting resin, impregnating a base material such as glass cloth with an epoxy resin varnish, and heating and drying. ) Is used.
【０００４】また、近年では上記のようなプリプレグに
代わって、銅箔などの金属箔にエポキシ樹脂などの熱硬
化性樹脂を塗布して半硬化状態（Ｂ−ステージ）に乾燥
して調製される樹脂付き銅箔も使用されている。このも
のではプリプレグの場合のような基材が存在しないの
で、プリント配線板や多層プリント配線板を軽量化、小
型化することができ、機器の軽量化や小型化に寄与する
ことができるものである。In recent years, instead of the above-described prepreg, a thermosetting resin such as an epoxy resin is applied to a metal foil such as a copper foil and dried in a semi-cured state (B-stage). Copper foil with resin is also used. In this case, since there is no base material as in the case of prepreg, it is possible to reduce the weight and size of printed wiring boards and multilayer printed wiring boards, which can contribute to the weight reduction and miniaturization of equipment. is there.
【０００５】そして近年のプリント配線板や多層プリン
ト配線板の小型化、高密度化に伴って配線密度の向上が
求められており、回路間の絶縁樹脂層の耐熱性の向上が
要求されている。[0005] With the recent miniaturization and high density of printed wiring boards and multilayer printed wiring boards, there is a demand for an increase in wiring density, and an improvement in heat resistance of an insulating resin layer between circuits is required. .
【０００６】[0006]
【発明が解決しようとする課題】上記のプリプレグや樹
脂付き金属箔のエポキシ樹脂は半硬化状態であるので、
プリプレグや樹脂付き金属箔を所定の大きさに切断する
際に、樹脂粉の飛散が発生し易い。そしてこの飛散した
樹脂粉が積層成形時に金属箔の表面に付着すると、回路
形成する際のエッチング工程などで樹脂粉の付着部分に
金属箔が残存し、絶縁性不良やショートなどの原因にな
るおそれがあり、プリント配線板や多層プリント配線板
の信頼性が低下するものであった。The epoxy resin of the above-mentioned prepreg or metal foil with resin is in a semi-cured state.
When a prepreg or a metal foil with resin is cut into a predetermined size, scattering of resin powder is likely to occur. If the scattered resin powder adheres to the surface of the metal foil at the time of lamination molding, the metal foil remains on the adhered portion of the resin powder in an etching step when forming a circuit, and may cause defective insulation or short circuit. Therefore, the reliability of the printed wiring board and the multilayer printed wiring board was reduced.
【０００７】特に、上記のように絶縁樹脂層の耐熱性の
向上を達成するためには、硬化樹脂の架橋密度を上げる
必要があり、このためにはエポキシ樹脂の官能基当量を
低くする必要があるが、官能基当量の低いエポキシ樹脂
を半硬化状態にしたものは樹脂の平均分子量が小さくな
って、切断時の樹脂粉の飛散が多くなる傾向にあり、上
記の問題が一層発生し易くなるものであった。In particular, in order to improve the heat resistance of the insulating resin layer as described above, it is necessary to increase the crosslink density of the cured resin, and for this purpose, it is necessary to reduce the functional group equivalent of the epoxy resin. However, in the case of a semi-cured epoxy resin having a low functional group equivalent, the average molecular weight of the resin is small, and the scattering of the resin powder at the time of cutting tends to increase, so that the above problem is more likely to occur. Was something.
【０００８】本発明は上記の点に鑑みてなされたもので
あり、切断時の樹脂粉の飛散が少ないエポキシ樹脂組成
物、プリプレグ、樹脂付き金属箔を提供することを目的
とするものであり、また信頼性の高いプリント配線板や
多層プリント配線板を得ることができる積層板を提供す
ることを目的とするものである。[0008] The present invention has been made in view of the above points, and an object of the present invention is to provide an epoxy resin composition, a prepreg, and a resin-attached metal foil with less scattering of resin powder during cutting. It is another object of the present invention to provide a laminated board from which a highly reliable printed wiring board or multilayer printed wiring board can be obtained.
【０００９】[0009]
【課題を解決するための手段】本発明の請求項１に係る
エポキシ樹脂組成物は、１分子中に３個以上のエポキシ
基を持つエポキシ樹脂と、ブタジエン−アクリロニトリ
ル共重合ゴムとを構成成分として含有して成ることを特
徴とするものである。The epoxy resin composition according to claim 1 of the present invention comprises an epoxy resin having three or more epoxy groups in one molecule and a butadiene-acrylonitrile copolymer rubber as constituents. It is characterized by comprising.
【００１０】また本発明の請求項２に係るエポキシ樹脂
組成物は、１分子中に３個以上のエポキシ基を持つエポ
キシ樹脂と、ポリビニルアセタール樹脂とを構成成分と
して含有して成ることを特徴とするものである。[0010] The epoxy resin composition according to a second aspect of the present invention is characterized in that it comprises an epoxy resin having three or more epoxy groups in one molecule and a polyvinyl acetal resin as constituents. Is what you do.
【００１１】また本発明の請求項３に係るエポキシ樹脂
組成物は、１分子中に３個以上のエポキシ基を持つエポ
キシ樹脂と、数平均分子量７０００〜１５０００のフェ
ノキシ樹脂とを構成成分として含有して成ることを特徴
とするものである。The epoxy resin composition according to claim 3 of the present invention comprises, as constituent components, an epoxy resin having three or more epoxy groups in one molecule and a phenoxy resin having a number average molecular weight of 7000 to 15,000. It is characterized by comprising.
【００１２】本発明の請求項４に係るプリプレグは、請
求項１〜３のいずれかに記載のエポキシ樹脂組成物を基
材に含浸して成ることを特徴とするものである。A prepreg according to a fourth aspect of the present invention is characterized in that a substrate is impregnated with the epoxy resin composition according to any one of the first to third aspects.
【００１３】本発明の請求項５に係る樹脂付き金属箔
は、請求項１〜３のいずれかに記載のエポキシ樹脂組成
物を金属箔の表面に塗布して成ることを特徴とするもの
である。A resin-coated metal foil according to a fifth aspect of the present invention is characterized in that the epoxy resin composition according to any one of the first to third aspects is applied to the surface of the metal foil. .
【００１４】本発明の請求項６に係る積層板は、請求項
４のプリプレグと請求項５の樹脂付き金属箔の少なくと
も一方を用いて積層成形して成ることを特徴とするもの
である。A laminate according to a sixth aspect of the present invention is characterized by being formed by lamination using at least one of the prepreg of the fourth aspect and the metal foil with resin of the fifth aspect.
【００１５】[0015]
【発明の実施の形態】以下、本発明の実施の形態を説明
する。Embodiments of the present invention will be described below.
【００１６】本発明においてエポキシ樹脂としては１分
子中に３個以上のエポキシ基を持つ３官能以上のものを
用いるものであり、このようなエポキシ樹脂であれば特
に制限されるものではないが、フェノールノボラック型
エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、
ナフタレン型エポキシ樹脂、ビスフェノールＡ型エポキ
シ樹脂や、これらを組み合わせたタイプのものを使用す
ることができる。１分子中のエポキシ基の数の上限は特
に設定されないが、実質的には１分子中のエポキシ基の
個数は１０個程度が上限である。この１分子中に３個以
上のエポキシ基を持つエポキシ樹脂は、エポキシ樹脂組
成物全量に対して５０〜９０重量％の配合量で用いるの
が好ましい。配合量がこの範囲より少ないと樹脂の耐熱
性が不足し、また配合量がこの範囲より多いと樹脂の可
撓性が低下して切断時の樹脂粉の発生を低減することが
難しくなる。In the present invention, as the epoxy resin, one having three or more functional groups having three or more epoxy groups in one molecule is used, and such an epoxy resin is not particularly limited. Phenol novolak epoxy resin, cresol novolak epoxy resin,
A naphthalene type epoxy resin, a bisphenol A type epoxy resin, or a combination thereof can be used. Although the upper limit of the number of epoxy groups in one molecule is not particularly set, the upper limit of the number of epoxy groups in one molecule is substantially about 10. The epoxy resin having three or more epoxy groups in one molecule is preferably used in an amount of 50 to 90% by weight based on the total amount of the epoxy resin composition. When the amount is less than this range, the heat resistance of the resin is insufficient, and when the amount is more than this range, the flexibility of the resin is reduced and it is difficult to reduce the generation of resin powder at the time of cutting.
【００１７】また、エポキシ樹脂としてはこの１分子中
に３個以上のエポキシ基を持つものの他に、１分子中に
２個のエポキシ基を持つエポキシ樹脂を併用することは
差し支えない。さらに難燃性を付与する目的で、臭素や
塩素などのハロゲン化合物を含有するエポキシ樹脂を使
用することも可能である。In addition to the epoxy resin having three or more epoxy groups in one molecule, the epoxy resin having two epoxy groups in one molecule may be used in combination. Further, for the purpose of imparting flame retardancy, it is also possible to use an epoxy resin containing a halogen compound such as bromine or chlorine.
【００１８】本発明において、エポキシ樹脂はその全体
としてのエポキシ当量が２００〜２０００になるように
するのが好ましい。エポキシ当量がこの範囲より極端に
大きいと、エポキシ樹脂の架橋度が低くなって耐熱性が
不足し、逆にこの範囲より小さいと、硬化剤の配合量が
多く必要になって、樹脂との相溶性が低下して硬化剤が
析出したり反応しない硬化剤が残留して、却って耐熱性
が不足するおそれがある。In the present invention, the epoxy resin preferably has an overall epoxy equivalent of 200 to 2,000. If the epoxy equivalent is extremely larger than this range, the degree of cross-linking of the epoxy resin will be low and heat resistance will be insufficient. Conversely, if the epoxy equivalent is smaller than this range, a large amount of the curing agent will be required, and the There is a possibility that the curing agent may precipitate due to the decrease in solubility or remain unreacted, so that the heat resistance may be insufficient.
【００１９】また、請求項１の発明で用いるブタジエン
−アクリロニトリル共重合ゴムとしては、結合アクリロ
ニトリル量が１０〜５０重量％のものが特に好ましい。
このブタジエン−アクリロニトリル共重合ゴムは必要に
応じて硫黄、過酸化物を使用して架橋することにより、
架橋ゴム化して使用してもよい。ブタジエン−アクリロ
ニトリル共重合ゴムの配合量は、エポキシ樹脂組成物の
樹脂固形分に対して３〜１０重量％の範囲が好ましい。
配合量がこの範囲より多いと、樹脂の耐熱性が低下した
り成形性が悪化するおそれがあり、逆に配合量がこの範
囲より少ないと、樹脂の可撓性を向上させる効果を十分
に得ることができず、Ｂステージ状態での切断時の樹脂
粉の飛散を十分に低減することができないものであり、
いずれも好ましくない。また樹脂の可撓性を高めて切断
時の樹脂粉の飛散を防止する目的で、高分子量のフェノ
キシ樹脂やポリビニルアセタール樹脂をこの共重合ゴム
と併用するようにしてもよい。The butadiene-acrylonitrile copolymer rubber used in the first aspect of the present invention is particularly preferably one having a bound acrylonitrile content of 10 to 50% by weight.
This butadiene-acrylonitrile copolymer rubber is optionally crosslinked using sulfur and peroxide,
It may be used as a crosslinked rubber. The compounding amount of the butadiene-acrylonitrile copolymer rubber is preferably in the range of 3 to 10% by weight based on the resin solid content of the epoxy resin composition.
When the amount is more than this range, the heat resistance of the resin may be reduced or the moldability may be deteriorated. On the contrary, when the amount is less than this range, the effect of improving the flexibility of the resin is sufficiently obtained. And the scattering of resin powder during cutting in the B-stage state cannot be sufficiently reduced,
Neither is preferred. For the purpose of increasing the flexibility of the resin and preventing the resin powder from scattering at the time of cutting, a high molecular weight phenoxy resin or polyvinyl acetal resin may be used in combination with this copolymer rubber.
【００２０】次に、請求項２の発明で用いるポリビニル
アセタール樹脂としては、ポリビニルホルマールやポリ
ビニルブチラールなどを使用することができる。このポ
リビニルアセタール樹脂のアセタール化量は７０〜９５
％のものが好ましく、アセタール化量がこの範囲よりも
高いものはポリビニルアセタール樹脂の合成が困難であ
り、アセタール化量がこの範囲より小さいものは樹脂の
耐熱性が低下すると共に樹脂粉の飛散防止の向上の効果
が十分に得ることができず、いずれも好ましくない。ポ
リビニルアセタール樹脂の配合量は、エポキシ樹脂組成
物の樹脂固形分に対して３〜１５重量％の範囲が好まし
い。配合量がこの範囲より少ないと、樹脂の可撓性を向
上させる効果を十分に得ることができず、Ｂステージ状
態での切断時の樹脂粉の飛散を十分に低減することがで
きないものであり、逆に配合量がこの範囲より多いと、
樹脂ワニスの粘度が高くなってプリプレグを作製する際
の基材への含浸や、樹脂付き金属箔を作製する際の金属
箔への塗布の作業性が悪くなったり、樹脂の耐熱性が低
下したりするおそれがあり、いずれも好ましくない。ま
た樹脂の可撓性を高めて切断時の樹脂粉の飛散を防止す
る目的で、ブタジエン−アクリロニトリル共重合ゴムな
どのゴム成分や高分子量のフェノキシ樹脂をこのポリビ
ニルアセタール樹脂と併用するようにしてもよい。Next, as the polyvinyl acetal resin used in the second aspect of the invention, polyvinyl formal, polyvinyl butyral and the like can be used. The acetalization amount of this polyvinyl acetal resin is 70 to 95.
% Is preferable. If the acetalization amount is higher than this range, it is difficult to synthesize a polyvinyl acetal resin. If the acetalization amount is smaller than this range, the heat resistance of the resin decreases and the resin powder is prevented from scattering. Cannot be sufficiently obtained, and both are not preferred. The compounding amount of the polyvinyl acetal resin is preferably in the range of 3 to 15% by weight based on the resin solid content of the epoxy resin composition. If the compounding amount is less than this range, the effect of improving the flexibility of the resin cannot be sufficiently obtained, and the scattering of the resin powder at the time of cutting in the B-stage state cannot be sufficiently reduced. Conversely, if the amount is more than this range,
As the viscosity of the resin varnish increases, impregnation of the base material when preparing a prepreg, or the workability of application to the metal foil when preparing a metal foil with resin deteriorates, or the heat resistance of the resin decreases. And there is a possibility that they are not preferable. Further, for the purpose of increasing the flexibility of the resin and preventing scattering of the resin powder at the time of cutting, a rubber component such as butadiene-acrylonitrile copolymer rubber or a high molecular weight phenoxy resin may be used in combination with the polyvinyl acetal resin. Good.
【００２１】次に、請求項３の発明で用いるフェノキシ
樹脂は数平均分子量７０００〜１５０００のものを使用
するものである。数平均分子量が７０００より低いフェ
ノキシ樹脂では樹脂の可撓性を高めることができず、切
断時の樹脂粉の飛散防止の向上効果を得ることができな
いものであり、数平均分子量が１５０００より高いフェ
ノキシ樹脂では、樹脂ワニスの粘度が高くなってプリプ
レグを作製する際の基材への含浸や、樹脂付き金属箔を
作製する際の金属箔への塗布の作業性が悪くなる。この
高分子量のフェノキシ樹脂の配合量は、エポキシ樹脂組
成物中の含有量が５〜２５重量％の範囲になるように設
定するのが好ましい。配合量がこの範囲より少ないと、
樹脂の可撓性を向上させる効果を十分に得ることができ
ず、Ｂステージ状態での切断時の樹脂粉の飛散を十分に
低減することができないものであり、逆に配合量がこの
範囲より多いと、樹脂の耐熱性が低下したり、樹脂ワニ
スの粘度が高くなってプリプレグを作製する際の基材へ
の含浸や、樹脂付き金属箔を作製する際の金属箔への塗
布の作業性が悪くなったりするおそれがあり、いずれも
好ましくない。また樹脂の可撓性を高めて切断時の樹脂
粉の飛散を防止する目的で、ブタジエン−アクリロニト
リル共重合ゴムなどのゴム成分やポリビニルアセタール
樹脂をこの高分子量のフェノキシ樹脂と併用するように
してもよい。The phenoxy resin used in the third aspect of the present invention has a number average molecular weight of 7,000 to 15,000. A phenoxy resin having a number average molecular weight of less than 7000 cannot increase the flexibility of the resin, failing to obtain an effect of preventing resin powder from scattering at the time of cutting, and a phenoxy resin having a number average molecular weight of more than 15,000. In the case of resin, the viscosity of the resin varnish becomes high, so that the workability of impregnating the base material when preparing a prepreg or coating the metal foil when preparing a metal foil with resin is deteriorated. The compounding amount of the high molecular weight phenoxy resin is preferably set so that the content in the epoxy resin composition is in the range of 5 to 25% by weight. If the amount is less than this range,
The effect of improving the flexibility of the resin cannot be sufficiently obtained, and the scattering of the resin powder at the time of cutting in the B-stage state cannot be sufficiently reduced. If too much, the heat resistance of the resin will decrease, or the viscosity of the resin varnish will increase, impregnating the base material when preparing a prepreg, and the workability of applying to the metal foil when preparing a metal foil with resin May be deteriorated, and both are not preferred. For the purpose of increasing the flexibility of the resin and preventing the resin powder from scattering at the time of cutting, a rubber component such as butadiene-acrylonitrile copolymer rubber or a polyvinyl acetal resin may be used in combination with the high-molecular-weight phenoxy resin. Good.
【００２２】そして、１分子中に３個以上のエポキシ基
を持つエポキシ樹脂に、請求項１の発明ではブタジエン
−アクリロニトリル共重合ゴムを配合し、請求項２の発
明ではポリビニルアセタール樹脂を配合し、請求項３の
発明では数平均分子量７０００〜１５０００のフェノキ
シ樹脂を配合し、さらにこれらに硬化剤を配合すること
によってエポキシ樹脂組成物を調製することができるも
のである。硬化剤としてはアミン系硬化剤、フェノール
系硬化剤、酸無水物系硬化剤などを用いることができる
ものであり、硬化剤の配合量はエポキシ樹脂組成物中１
〜５０重量％の範囲が好ましい。またこれらのエポキシ
樹脂組成物には、難燃性を付与する目的で、ハロゲン化
合物を配合することもできる。ハロゲン化合物を配合す
る場合にはその配合量はエポキシ樹脂組成物の全量に対
して１０〜３０重量％の範囲が好ましい。この範囲より
少ないと難燃性を付与する効果が小さく、この範囲より
多いと熱時のハロゲンの分解による耐熱性の低下が起こ
るので、好ましくない。In the invention of claim 1, butadiene-acrylonitrile copolymer rubber is blended with an epoxy resin having three or more epoxy groups in one molecule, and in the invention of claim 2, polyvinyl acetal resin is blended. According to the third aspect of the present invention, an epoxy resin composition can be prepared by blending a phenoxy resin having a number average molecular weight of 7000 to 15000, and further blending a curing agent therewith. As the curing agent, an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, or the like can be used, and the amount of the curing agent is 1 in the epoxy resin composition.
The range of ５０50% by weight is preferred. In addition, a halogen compound can be added to these epoxy resin compositions for the purpose of imparting flame retardancy. When a halogen compound is compounded, the compounding amount is preferably in the range of 10 to 30% by weight based on the total amount of the epoxy resin composition. If it is less than this range, the effect of imparting flame retardancy is small, and if it is more than this range, the heat resistance is reduced due to the decomposition of halogen during heating, which is not preferable.
【００２３】上記のエポキシ樹脂組成物を溶剤に溶解し
て希釈することによって、樹脂ワニスを調製することが
できる。そしてこの樹脂ワニスを基材に含浸し、乾燥機
中で１２０〜１９０℃程度の温度で３〜１５分間程度乾
燥することによって、樹脂を半硬化状態（Ｂ−ステー
ジ）にしたプリプレグを作製することができる。ここで
基材としてはガラスクロス、ガラスペーパー、ガラスマ
ットなどのガラス繊維布の他、クラフト紙、リンター
紙、天然繊維布、合成繊維布などを用いることができ
る。A resin varnish can be prepared by dissolving and diluting the above epoxy resin composition in a solvent. Then, the resin varnish is impregnated into a substrate, and dried in a dryer at a temperature of about 120 to 190 ° C. for about 3 to 15 minutes to produce a prepreg in which the resin is in a semi-cured state (B-stage). Can be. Here, as a substrate, kraft paper, linter paper, natural fiber cloth, synthetic fiber cloth, or the like can be used in addition to glass fiber cloth such as glass cloth, glass paper, and glass mat.
【００２４】また上記の樹脂ワニスを銅箔、銀箔、アル
ミニウム箔、ステンレス箔等の金属箔の表面に塗布し、
乾燥機中で１２０〜１９０℃程度の温度で３〜１５分間
程度乾燥することによって、半硬化状態（Ｂ−ステー
ジ）の樹脂層を表面に設けた樹脂付き金属箔を作製する
ことができる。The above resin varnish is applied to the surface of a metal foil such as a copper foil, a silver foil, an aluminum foil and a stainless steel foil,
By drying in a dryer at a temperature of about 120 to 190 ° C. for about 3 to 15 minutes, a resin-attached metal foil having a resin layer in a semi-cured state (B-stage) provided on the surface can be produced.
【００２５】ここで、上記のようにして得られるプリプ
レグや樹脂付き金属箔にあって、エポキシ樹脂組成物
は、１分子中に３個以上のエポキシ基を持つエポキシ樹
脂に、ブタジエン−アクリロニトリル共重合ゴムや、ポ
リビニルアセタール樹脂や、数平均分子量７０００〜１
５０００のフェノキシ樹脂が配合してあるために、プリ
プレグや樹脂付き金属箔の半硬化状態の樹脂は可撓性が
高められており、プリプレグや樹脂付き金属箔を所定寸
法に切断するにあたって、樹脂粉が飛散することを低減
することができるものである。Here, in the prepreg or resin-coated metal foil obtained as described above, the epoxy resin composition is prepared by adding butadiene-acrylonitrile copolymer to an epoxy resin having three or more epoxy groups in one molecule. Rubber, polyvinyl acetal resin, number average molecular weight 7000-1
Because the phenoxy resin of 5000 is blended, the flexibility of the semi-cured resin of the prepreg or the resin-coated metal foil is enhanced, and when cutting the prepreg or the resin-coated metal foil to a predetermined size, the resin powder is used. Can be reduced.
【００２６】次に、上記のようにして調製したプリプレ
グを所要枚数重ね、これを１４０〜２００℃、１０〜５
０ｋｇ／ｃｍ2、４０〜１５０分の条件で加熱加圧して
積層成形することによって、積層板を製造することがで
きる。この際に、所要枚数重ねたプリプレグの片側もし
くは両側に金属箔を重ねて積層成形することによって、
プリント配線板に加工するための金属箔張り積層板を製
造することができる。この金属箔としては、銅箔、銀
箔、アルミニウム箔、ステンレス箔などを用いることが
できる。Next, a required number of prepregs prepared as described above are stacked,
A laminate can be manufactured by heating and pressing under the conditions of 0 kg / cm 2 and 40 to 150 minutes to form a laminate. At this time, by laminating metal foil on one side or both sides of the required number of prepreg,
A metal foil-clad laminate for processing into a printed wiring board can be manufactured. As the metal foil, a copper foil, a silver foil, an aluminum foil, a stainless steel foil, or the like can be used.
【００２７】また、予め内層用の回路を形成した内層回
路板の片側もしくは両側に所要枚数のプリプレグを重ね
ると共にその外側に金属箔を配置し、これを加熱加圧し
て積層成形することによって、多層プリント配線板に加
工するための多層積層板を製造することができる。この
ように多層積層板を製造する際には、プリプレグによる
絶縁樹脂層との密着性を高めるために、内層回路板の内
層回路を構成する銅箔の表面を黒化処理等の化学的な処
理によって酸化銅にしており、このために成形時の温度
は１５０〜１８０℃の範囲に設定するのが好ましい。成
形温度が１５０℃未満では、プリプレグの硬化が不十分
になって耐熱性を十分に得ることが難しく、またプリプ
レグによる絶縁樹脂層と内層回路の銅箔との接着強度が
不十分になるおそれがある。逆に成形温度が１８０℃を
超えると、内層回路の銅箔の表面を酸化銅にすることに
よって生じる凹凸が消失し、プリプレグによる絶縁樹脂
層と内層回路の銅箔との接着強度が不十分になるおそれ
がある。Further, a required number of prepregs are stacked on one or both sides of an inner circuit board on which an inner layer circuit has been formed in advance, and a metal foil is arranged outside the prepreg. A multilayer laminate for processing into a printed wiring board can be manufactured. When manufacturing a multilayer laminate in this way, in order to enhance the adhesion between the prepreg and the insulating resin layer, the surface of the copper foil constituting the inner layer circuit of the inner layer circuit board is subjected to a chemical treatment such as a blackening process. Therefore, the temperature at the time of molding is preferably set in the range of 150 to 180 ° C. When the molding temperature is lower than 150 ° C., the prepreg is hardened insufficiently and it is difficult to obtain sufficient heat resistance, and the adhesive strength between the insulating resin layer and the copper foil of the inner layer circuit by the prepreg may be insufficient. is there. Conversely, if the molding temperature exceeds 180 ° C., the irregularities caused by turning the surface of the copper foil of the inner layer circuit into copper oxide disappear, and the adhesive strength between the insulating resin layer and the copper foil of the inner layer circuit by the prepreg becomes insufficient. Could be.
【００２８】一方、予め内層用の回路を形成した内層回
路板の片側もしくは両側に上記の樹脂付き金属箔を樹脂
層の側で重ね、これを１４０〜２００℃、１０〜５０ｋ
ｇ／ｃｍ2、４０〜１５０分の条件で加熱加圧して積層
成形することによって、多層プリント配線板に加工する
ための多層積層板を製造することができる。On the other hand, the above-mentioned metal foil with resin is laminated on one side or both sides of the inner layer circuit board on which the circuit for the inner layer has been previously formed on the side of the resin layer.
By heating and pressurizing under the conditions of g / cm 2 and 40 to 150 minutes to perform lamination molding, a multilayer laminate for processing into a multilayer printed wiring board can be manufactured.
【００２９】上記のようにして得られた積層板（多層積
層板を含む）は、可撓性を高めた半硬化樹脂からなるプ
リプレグや樹脂付き金属箔によって形成されるものであ
り、上記のようにプリプレグや樹脂付き金属箔は切断時
の樹脂粉の発生が低減されており、この積層板を加工し
てプリント配線板（多層プリント配線板を含む）を製造
するにあたって、回路形成する際のエッチング工程など
で樹脂粉の付着部分に金属箔が残存するような問題がな
くなり、絶縁性不良やショートなどを未然に防いでプリ
ント配線板の信頼性を高めることができるものである。The laminate (including the multilayer laminate) obtained as described above is formed of a prepreg made of a semi-cured resin having enhanced flexibility or a metal foil with a resin. Pre-preg and metal foil with resin reduce the generation of resin powder when cutting. When processing this laminated board to manufacture printed wiring boards (including multilayer printed wiring boards), etching during circuit formation This eliminates the problem that the metal foil remains on the portion where the resin powder is adhered in the process or the like, and can prevent poor insulation or short-circuiting, thereby improving the reliability of the printed wiring board.
【００３０】[0030]
【実施例】以下本発明を実施例によって具体的に説明す
る。The present invention will be described below in detail with reference to examples.
【００３１】（実施例１）エポキシ樹脂として、３官能
のトリスフェノール型エポキシ樹脂（三井化学工業社製
「ＶＦ２８０２」：エポキシ当量３８０）９０．４ｇを
メチルエチルケトン（ＭＥＫ）で希釈して固形分濃度を
８０重量％にしたもの１１３ｇと、多官能のクレゾール
ノボラック型エポキシ樹脂（東都化成社製「ＹＤＣＮ−
７０４」：エポキシ当量２２０）１０ｇをＭＥＫで希釈
して固形分濃度を８０重量％にしたもの１２．５ｇを用
い、これにブタジエン−アクリロニトリル共重合ゴム
（日本合成ゴム社製「Ｎ２２０」：結合アクリロニトリ
ル量４１重量％）７ｇをＭＥＫで希釈して固形分濃度を
１０重量％にしたもの７０ｇと、ジシアンジアミド１．
９ｇをジメチルホルムアミド１０ｇで溶解した溶液を加
え、そしてさらにこれをＭＥＫで希釈して固形分濃度を
３０重量％にしたエポキシ樹脂ワニスを調製した。Example 1 As an epoxy resin, 90.4 g of a trifunctional trisphenol type epoxy resin (“VF2802” manufactured by Mitsui Chemicals, Inc .: epoxy equivalent: 380) was diluted with methyl ethyl ketone (MEK) to obtain a solid content concentration. 113 g of 80% by weight and a polyfunctional cresol novolak type epoxy resin (“YDCN-
704 ": 12.5 g of 10 g of an epoxy equivalent 220) diluted with MEK to a solid content of 80% by weight was used, and butadiene-acrylonitrile copolymer rubber (" N220 "manufactured by Nippon Synthetic Rubber Co., Ltd .: bound acrylonitrile) was used. (Amount of 41% by weight) was diluted with MEK to a solid content concentration of 10% by weight, and 70 g of dicyandiamide.
A solution in which 9 g was dissolved in 10 g of dimethylformamide was added, and the solution was further diluted with MEK to prepare an epoxy resin varnish having a solid content concentration of 30% by weight.
【００３２】次にこのエポキシ樹脂ワニスを１８μｍ厚
の銅箔の片面に塗布し、１５０℃で５分間乾燥すること
によって、厚み６０μｍの樹脂付き銅箔を作製した。こ
の樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛散量を
測定したところ、０．４ｍｇ／ｍ（折り曲げ長さ１ｍ当
たりの樹脂飛散量）であった。Next, this epoxy resin varnish was applied to one surface of a copper foil having a thickness of 18 μm, and dried at 150 ° C. for 5 minutes to produce a copper foil with a resin having a thickness of 60 μm. This resin-coated copper foil was bent at 180 ° and the scattering amount of the resin powder was measured. As a result, it was 0.4 mg / m (the resin scattering amount per bending length of 1 m).
【００３３】また、予め厚み３５μｍの銅箔で内層用の
回路を表面に形成した内層回路板（絶縁樹脂層の板厚
０．８ｍｍ）の両面に樹脂付き銅箔を樹脂の側で重ね、
１７０℃、３０ｋｇ／ｃｍ2、９０分間の条件で加熱加
圧して積層成形して、多層銅張り積層板を作製した。こ
の多層銅張り積層板の銅箔をエッチング除去して硬化樹
脂を露出させて観察したところ、ボイドやカスレなどの
不良はみられず、成形性は良好であった。またこの硬化
樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測定したと
ころ、１８０℃であった。Also, a resin-coated copper foil is laminated on both sides of an inner circuit board (0.8 mm thick insulating resin layer) in which a circuit for the inner layer is formed on the surface with a copper foil having a thickness of 35 μm in advance.
Laminate molding was performed by heating and pressing at 170 ° C., 30 kg / cm 2 for 90 minutes to produce a multilayer copper-clad laminate. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of this cured resin was 180 ° C. as measured by the TMA method.
【００３４】（実施例２）実施例１で得たエポキシ樹脂
ワニスをガラスクロス（ＭＩＬ規格２１１６タイプ）に
含浸し、１５０℃で５分間乾燥することによって、樹脂
量が４６重量％のプリプレグを作製した。このプリプレ
グを１８０°折り曲げて樹脂粉の飛散量を測定したとこ
ろ、１．５ｍｇ／ｍであった。(Example 2) A glass cloth (MIL standard 2116 type) was impregnated with the epoxy resin varnish obtained in Example 1 and dried at 150 ° C for 5 minutes to prepare a prepreg having a resin amount of 46% by weight. did. This prepreg was bent at 180 ° and the scattering amount of the resin powder was measured to be 1.5 mg / m.
【００３５】次にこのプリプレグを８枚重ね、両側に１
８μｍ厚の銅箔を配し、１７０℃、３０ｋｇ／ｃｍ2、
９０分間の条件で加熱加圧して積層成形して、銅張り積
層板を作製した。この銅張り積層板の銅箔をエッチング
除去して硬化樹脂を露出させて観察したところ、ボイド
やカスレなどの不良はみられず、成形性は良好であっ
た。またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭ
Ａ法で測定したところ、１７７℃であった。Next, eight prepregs are stacked, and one on each side.
A copper foil having a thickness of 8 μm is placed, and 170 ° C., 30 kg / cm 2 ,
Laminate molding was performed by heating and pressing under the conditions of 90 minutes to produce a copper-clad laminate. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. Further, the glass transition temperature (Tg) of this cured resin is set to TM
It was 177 ° C. as measured by Method A.
【００３６】（実施例３）ブタジエン−アクリロニトリ
ル共重合ゴムとして、日本合成ゴム社製「Ｎ２６０」
（結合アクリロニトリル量１５重量％）を用いるように
した他は、実施例１と同様にしてエポキシ樹脂ワニスを
調製した。Example 3 As a butadiene-acrylonitrile copolymer rubber, "N260" manufactured by Nippon Synthetic Rubber Co., Ltd.
An epoxy resin varnish was prepared in the same manner as in Example 1 except that (the amount of bound acrylonitrile was 15% by weight).
【００３７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、１．２ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 1 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° and the scattering amount of the resin powder was measured to be 1.2 mg / m.
【００３８】また、この樹脂付き銅箔を用いるようにし
た他は実施例１と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
などの不良はみられず、成形性は良好であった。またこ
の硬化樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測定
したところ、１８２℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 1 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of the cured resin was 182 ° C. as measured by the TMA method.
【００３９】（実施例４）実施例３で得たエポキシ樹脂
ワニスを用いるようにした他は実施例２と同様にしてプ
リプレグを作製した。このプリプレグを１８０°折り曲
げて樹脂粉の飛散量を測定したところ、２．５ｍｇ／ｍ
であった。Example 4 A prepreg was prepared in the same manner as in Example 2 except that the epoxy resin varnish obtained in Example 3 was used. When this prepreg was bent 180 ° and the amount of resin powder scattered was measured, it was 2.5 mg / m 2.
Met.
【００４０】次にこのプリプレグを用いるようにした他
は実施例２と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレなどの不良は
みられず、成形性は良好であった。またこの硬化樹脂の
ガラス転移温度（Ｔｇ）をＴＭＡ法で測定したところ、
１７９℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 2 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. When the glass transition temperature (Tg) of this cured resin was measured by the TMA method,
179 ° C.
【００４１】（実施例５）ブタジエン−アクリロニトリ
ル共重合ゴム（日本合成ゴム社製「Ｎ２２０」：結合ア
クリロニトリル量４１重量％）１８ｇをＭＥＫで希釈し
て固形分濃度を１０重量％にしたもの１８０ｇを使用す
るようにした他は、実施例１と同様にしてエポキシ樹脂
ワニスを調製した。Example 5 18 g of a butadiene-acrylonitrile copolymer rubber ("N220" manufactured by Nippon Synthetic Rubber Co., Ltd .: bound acrylonitrile amount: 41% by weight) was diluted with MEK to a solids concentration of 10% by weight, and 180 g of this was diluted. An epoxy resin varnish was prepared in the same manner as in Example 1 except that the varnish was used.
【００４２】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、０．３ｍｇ／ｍであった。Next, a resin-coated copper foil was produced in the same manner as in Example 1 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 0.3 mg / m.
【００４３】また、この樹脂付き銅箔を用いるようにし
た他は実施例１と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
がみられた。またこの硬化樹脂のガラス転移温度（Ｔ
ｇ）をＴＭＡ法で測定したところ、１７３℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 1 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed. Also, the glass transition temperature (T
g) was 173 ° C. as measured by the TMA method.
【００４４】（実施例６）実施例５で得たエポキシ樹脂
ワニスを用いるようにした他は実施例２と同様にしてプ
リプレグを作製した。このプリプレグを１８０°折り曲
げて樹脂粉の飛散量を測定したところ、１．０ｍｇ／ｍ
であった。(Example 6) A prepreg was prepared in the same manner as in Example 2 except that the epoxy resin varnish obtained in Example 5 was used. This prepreg was bent at 180 ° and the scattering amount of the resin powder was measured to be 1.0 mg / m 2
Met.
【００４５】次にこのプリプレグを用いるようにした他
は実施例２と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレがみられた。
またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法
で測定したところ、１６８℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 2 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed.
The glass transition temperature (Tg) of the cured resin was 168 ° C. as measured by the TMA method.
【００４６】（比較例１）ブタジエン−アクリロニトリ
ル共重合ゴムを使用せず、固形分濃度を５０重量％にす
るようにした他は実施例１と同様にしてエポキシ樹脂ワ
ニスを調製した。Comparative Example 1 An epoxy resin varnish was prepared in the same manner as in Example 1 except that the butadiene-acrylonitrile copolymer rubber was not used and the solid content concentration was adjusted to 50% by weight.
【００４７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、３７ｍｇ／ｍであった。Next, a resin-coated copper foil was produced in the same manner as in Example 1 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 37 mg / m.
【００４８】また、この樹脂付き銅箔を用いるようにし
た他は実施例１と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
などの不良はみられなかった。またこの硬化樹脂のガラ
ス転移温度（Ｔｇ）をＴＭＡ法で測定したところ、１７
９℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 1 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids and blurring were found. When the glass transition temperature (Tg) of the cured resin was measured by the TMA method,
9 ° C.
【００４９】（比較例２）比較例１で得たエポキシ樹脂
ワニスを用いるようにした他は実施例２と同様にしてプ
リプレグを作製した。このプリプレグを１８０°折り曲
げて樹脂粉の飛散量を測定したところ、１０２ｍｇ／ｍ
であった。Comparative Example 2 A prepreg was prepared in the same manner as in Example 2 except that the epoxy resin varnish obtained in Comparative Example 1 was used. When this prepreg was bent 180 ° and the amount of resin powder scattered was measured, it was 102 mg / m 2.
Met.
【００５０】次にこのプリプレグを用いるようにした他
は実施例２と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレなどの不良は
みられなかった。またこの硬化樹脂のガラス転移温度
（Ｔｇ）をＴＭＡ法で測定したところ、１７６℃であっ
た。Next, a copper-clad laminate was produced in the same manner as in Example 2 except that this prepreg was used. When the copper foil of the copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids or blurring were found. The glass transition temperature (Tg) of the cured resin measured by the TMA method was 176 ° C.
【００５１】[0051]
【表１】 （実施例７）エポキシ樹脂として、３官能のトリスフェ
ノール型エポキシ樹脂（三井化学工業社製「ＶＦ２８０
２」：エポキシ当量３８０）９０．４ｇをメチルエチル
ケトン（ＭＥＫ）で希釈して固形分濃度を８０重量％に
したもの１１３ｇと、多官能のクレゾールノボラック型
エポキシ樹脂（東都化成社製「ＹＤＣＮ−７０４」：エ
ポキシ当量２２０）１０ｇをＭＥＫで希釈して固形分濃
度を８０重量％にしたもの１２．５ｇを用い、これにポ
リビニルアセタール樹脂（電気化学工業社製「６０００
ＡＳ」：アセタール化量９１％）１０ｇを撹拌しながら
添加し、さらにジシアンジアミド１．９ｇをジメチルホ
ルムアミド１０ｇで溶解した溶液を加え、そしてさらに
これをＭＥＫで希釈して固形分濃度を３０重量％にした
エポキシ樹脂ワニスを調製した。[Table 1] (Example 7) As an epoxy resin, a trifunctional trisphenol type epoxy resin ("VF280" manufactured by Mitsui Chemicals, Inc.)
2 ": 113 g obtained by diluting 90.4 g of an epoxy equivalent (380) with methyl ethyl ketone (MEK) to a solid concentration of 80% by weight, and a polyfunctional cresol novolak type epoxy resin (" YDCN-704 "manufactured by Toto Kasei Co., Ltd.) : Epoxy equivalent 220) 12.5 g obtained by diluting 10 g with MEK to a solid content concentration of 80% by weight, and using polyvinyl acetal resin (“6000” manufactured by Denki Kagaku Kogyo KK)
AS ": 91% of acetalized amount) was added with stirring, a solution of 1.9 g of dicyandiamide dissolved in 10 g of dimethylformamide was added, and this was further diluted with MEK to a solid content concentration of 30% by weight. The prepared epoxy resin varnish was prepared.
【００５２】次にこのエポキシ樹脂ワニスを１８μｍ厚
の銅箔の片面に塗布し、１５０℃で５分間乾燥すること
によって、厚み６０μｍの樹脂付き銅箔を作製した。こ
の樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛散量を
測定したところ、０．１５ｍｇ／ｍであった。Next, this epoxy resin varnish was applied to one surface of a copper foil having a thickness of 18 μm and dried at 150 ° C. for 5 minutes to produce a copper foil with a resin having a thickness of 60 μm. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 0.15 mg / m.
【００５３】また、予め厚み３５μｍの銅箔で内層用の
回路を表面に形成した内層回路板（絶縁樹脂層の板厚
０．８ｍｍ）の両面に樹脂付き銅箔を樹脂の側で重ね、
１７０℃、３０ｋｇ／ｃｍ2、９０分間の条件で加熱加
圧して積層成形して、多層銅張り積層板を作製した。こ
の多層銅張り積層板の銅箔をエッチング除去して硬化樹
脂を露出させて観察したところ、ボイドやカスレなどの
不良はみられず、成形性は良好であった。またこの硬化
樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測定したと
ころ、１７９℃であった。In addition, a resin-coated copper foil is superposed on both sides of an inner circuit board (0.8 mm thick insulating resin layer) in which a circuit for the inner layer is previously formed on the surface with a copper foil having a thickness of 35 μm.
Laminate molding was performed by heating and pressing at 170 ° C., 30 kg / cm 2 for 90 minutes to produce a multilayer copper-clad laminate. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of this cured resin was 179 ° C. as measured by the TMA method.
【００５４】（実施例８）実施例７で得たエポキシ樹脂
ワニスをガラスクロス（ＭＩＬ規格２１１６タイプ）に
含浸し、１５０℃で５分間乾燥することによって、樹脂
量が４６重量％のプリプレグを作製した。このプリプレ
グを１８０°折り曲げて樹脂粉の飛散量を測定したとこ
ろ、０．５ｍｇ／ｍであった。(Example 8) A glass cloth (MIL standard 2116 type) was impregnated with the epoxy resin varnish obtained in Example 7 and dried at 150 ° C for 5 minutes to prepare a prepreg having a resin amount of 46% by weight. did. This prepreg was bent at 180 ° and the scattering amount of the resin powder was measured to be 0.5 mg / m.
【００５５】次にこのプリプレグを８枚重ね、両側に１
８μｍ厚の銅箔を配し、１７０℃、３０ｋｇ／ｃｍ2、
９０分間の条件で加熱加圧して積層成形して、銅張り積
層板を作製した。この銅張り積層板の銅箔をエッチング
除去して硬化樹脂を露出させて観察したところ、ボイド
やカスレなどの不良はみられず、成形性は良好であっ
た。またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭ
Ａ法で測定したところ、１７２℃であった。Next, eight prepregs were stacked, and one on each side.
A copper foil having a thickness of 8 μm is placed, and 170 ° C., 30 kg / cm 2 ,
Laminate molding was performed by heating and pressing under the conditions of 90 minutes to produce a copper-clad laminate. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. Further, the glass transition temperature (Tg) of this cured resin is set to TM
It was 172 ° C. as measured by Method A.
【００５６】（実施例９）ポリビニルアセタール樹脂と
して、電気化学工業社製「６０００ＡＰ」（アセタール
化量７３％）を用いるようにした他は、実施例１と同様
にしてエポキシ樹脂ワニスを調製した。Example 9 An epoxy resin varnish was prepared in the same manner as in Example 1 except that "6000AP" (acetalization amount: 73%) manufactured by Denki Kagaku Kogyo was used as the polyvinyl acetal resin.
【００５７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例７と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、１．０ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 7 except that the epoxy resin varnish was used. When this resin-coated copper foil was bent at 180 ° and the amount of resin powder scattered was measured, it was 1.0 mg / m.
【００５８】また、この樹脂付き銅箔を用いるようにし
た他は実施例７と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
などの不良はみられず、成形性は良好であった。またこ
の硬化樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測定
したところ、１７６℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 7 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of the cured resin measured by the TMA method was 176 ° C.
【００５９】（実施例１０）実施例９で得たエポキシ樹
脂ワニスを用いるようにした他は実施例８と同様にして
プリプレグを作製した。このプリプレグを１８０°折り
曲げて樹脂粉の飛散量を測定したところ、２．７ｍｇ／
ｍであった。(Example 10) A prepreg was prepared in the same manner as in Example 8, except that the epoxy resin varnish obtained in Example 9 was used. When this prepreg was bent 180 ° and the amount of resin powder scattered was measured, 2.7 mg /
m.
【００６０】次にこのプリプレグを用いるようにした他
は実施例８と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレなどの不良は
みられず、成形性は良好であった。またこの硬化樹脂の
ガラス転移温度（Ｔｇ）をＴＭＡ法で測定したところ、
１７１℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 8 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. When the glass transition temperature (Tg) of this cured resin was measured by the TMA method,
171 ° C.
【００６１】（実施例１１）ポリビニルアセタール樹脂
（電気化学工業社製「６０００ＡＳ」：アセタール化量
９１％）２７ｇを使用するようにした他は、実施例７と
同様にしてエポキシ樹脂ワニスを調製した。Example 11 An epoxy resin varnish was prepared in the same manner as in Example 7, except that 27 g of polyvinyl acetal resin ("6000AS" manufactured by Denki Kagaku Kogyo Co., Ltd., acetalization amount: 91%) was used. .
【００６２】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例７と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、０．０７ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 7, except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 0.07 mg / m.
【００６３】また、この樹脂付き銅箔を用いるようにし
た他は実施例７と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
がみられた。またこの硬化樹脂のガラス転移温度（Ｔ
ｇ）をＴＭＡ法で測定したところ、１６５℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 7, except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed. Also, the glass transition temperature (T
g) was 165 ° C. as measured by the TMA method.
【００６４】（実施例１２）実施例１１で得たエポキシ
樹脂ワニスを用いるようにした他は実施例８と同様にし
てプリプレグを作製した。このプリプレグを１８０°折
り曲げて樹脂粉の飛散量を測定したところ、０．３ｍｇ
／ｍであった。(Example 12) A prepreg was prepared in the same manner as in Example 8, except that the epoxy resin varnish obtained in Example 11 was used. This prepreg was bent at 180 ° and the scattering amount of the resin powder was measured.
/ M.
【００６５】次にこのプリプレグを用いるようにした他
は実施例８と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレがみられた。
またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法
で測定したところ、１６１℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 8 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed.
The glass transition temperature (Tg) of the cured resin was 161 ° C. as measured by the TMA method.
【００６６】（比較例３）ポリビニルアセタール樹脂を
使用せず、固形分濃度を５０重量％にするようにした他
は実施例７と同様にしてエポキシ樹脂ワニスを調製し
た。Comparative Example 3 An epoxy resin varnish was prepared in the same manner as in Example 7, except that the polyvinyl acetal resin was not used and the solid content was adjusted to 50% by weight.
【００６７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例７と同様にして樹脂付き銅箔を作製し
た。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛
散量を測定したところ、３８ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 7 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 38 mg / m.
【００６８】また、この樹脂付き銅箔を用いるようにし
た他は実施例７と同様にして多層銅張り積層板を作製し
た。この多層銅張り積層板の銅箔をエッチング除去して
硬化樹脂を露出させて観察したところ、ボイドやカスレ
などの不良はみられなかった。またこの硬化樹脂のガラ
ス転移温度（Ｔｇ）をＴＭＡ法で測定したところ、１７
７℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 7 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids and blurring were found. When the glass transition temperature (Tg) of the cured resin was measured by the TMA method,
7 ° C.
【００６９】（比較例４）比較例３で得たエポキシ樹脂
ワニスを用いるようにした他は実施例８と同様にしてプ
リプレグを作製した。このプリプレグを１８０°折り曲
げて樹脂粉の飛散量を測定したところ、１９６ｍｇ／ｍ
であった。Comparative Example 4 A prepreg was prepared in the same manner as in Example 8, except that the epoxy resin varnish obtained in Comparative Example 3 was used. This prepreg was bent at 180 ° and the amount of resin powder scattered was measured to be 196 mg / m
Met.
【００７０】次にこのプリプレグを用いるようにした他
は実施例８と同様にして銅張り積層板を作製した。この
銅張り積層板の銅箔をエッチング除去して硬化樹脂を露
出させて観察したところ、ボイドやカスレなどの不良は
みられなかった。またこの硬化樹脂のガラス転移温度
（Ｔｇ）をＴＭＡ法で測定したところ、１７６℃であっ
た。Next, a copper-clad laminate was produced in the same manner as in Example 8 except that this prepreg was used. When the copper foil of the copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids or blurring were found. The glass transition temperature (Tg) of the cured resin measured by the TMA method was 176 ° C.
【００７１】[0071]
【表２】 （実施例１３）エポキシ樹脂として、３官能のトリスフ
ェノール型エポキシ樹脂（三井化学工業社製「ＶＦ２８
０２」：エポキシ当量３８０）９０．４ｇをメチルエチ
ルケトン（ＭＥＫ）で希釈して固形分濃度を８０重量％
にしたもの１１３ｇと、多官能のクレゾールノボラック
型エポキシ樹脂（東都化成社製「ＹＤＣＮ−７０４」：
エポキシ当量２２０）１０ｇをＭＥＫで希釈して固形分
濃度を８０重量％にしたもの１２．５ｇを用い、これに
フェノキシ樹脂（東都化成社製：数平均分子量８３０
０）１９．２ｇをＭＥＫで希釈して固形分濃度を４０重
量％にしたもの４８ｇと、ジシアンジアミド１．９ｇを
ジメチルホルムアミド１０ｇで溶解した溶液を加え、そ
してさらにこれをＭＥＫで希釈して固形分濃度を４０重
量％にしたエポキシ樹脂ワニスを調製した。[Table 2] (Example 13) As an epoxy resin, a trifunctional trisphenol-type epoxy resin ("VF28" manufactured by Mitsui Chemicals, Inc.)
02 ": 90.4 g of epoxy equivalent (380) was diluted with methyl ethyl ketone (MEK) to give a solid content of 80% by weight.
And 113 g of a polyfunctional cresol novolak type epoxy resin (“YDCN-704” manufactured by Toto Kasei Co., Ltd.)
12.5 g of 10 g of an epoxy equivalent (220) diluted with MEK to a solid concentration of 80% by weight was used, and phenoxy resin (manufactured by Toto Kasei Co., Ltd .: number average molecular weight 830) was used.
0) 19.2 g was diluted with MEK to a solid content concentration of 40% by weight, 48 g, and a solution of 1.9 g of dicyandiamide dissolved in 10 g of dimethylformamide were added thereto. An epoxy resin varnish having a concentration of 40% by weight was prepared.
【００７２】次にこのエポキシ樹脂ワニスを１８μｍ厚
の銅箔の片面に塗布し、１５０℃で５分間乾燥すること
によって、厚み６０μｍの樹脂付き銅箔を作製した。こ
の樹脂付き銅箔を１８０°折り曲げて樹脂粉の飛散量を
測定したところ、０．４ｍｇ／ｍであった。Next, this epoxy resin varnish was applied to one surface of a copper foil having a thickness of 18 μm and dried at 150 ° C. for 5 minutes to produce a copper foil with a resin having a thickness of 60 μm. This resin-coated copper foil was bent at 180 ° and the scattering amount of the resin powder was measured to be 0.4 mg / m.
【００７３】また、予め厚み３５μｍの銅箔で内層用の
回路を表面に形成した内層回路板（絶縁樹脂層の板厚
０．８ｍｍ）の両面に樹脂付き銅箔を樹脂の側で重ね、
１７０℃、３０ｋｇ／ｃｍ2、９０分間の条件で加熱加
圧して積層成形して、多層銅張り積層板を作製した。こ
の多層銅張り積層板の銅箔をエッチング除去して硬化樹
脂を露出させて観察したところ、ボイドやカスレなどの
不良はみられず、成形性は良好であった。またこの硬化
樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測定したと
ころ、１７８℃であった。Further, a resin-coated copper foil is laminated on both sides of an inner layer circuit board (insulating resin layer having a thickness of 0.8 mm) in which a circuit for an inner layer is formed on the surface with a copper foil having a thickness of 35 μm in advance.
Laminate molding was performed by heating and pressing at 170 ° C., 30 kg / cm 2 for 90 minutes to produce a multilayer copper-clad laminate. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of this cured resin was 178 ° C. as measured by the TMA method.
【００７４】（実施例１４）実施例１３で得たエポキシ
樹脂ワニスをガラスクロス（ＭＩＬ規格２１１６タイ
プ）に含浸し、１５０℃で５分間乾燥することによっ
て、樹脂量が４６重量％のプリプレグを作製した。この
プリプレグを１８０°折り曲げて樹脂粉の飛散量を測定
したところ、１．６ｍｇ／ｍであった。Example 14 A glass cloth (MIL standard 2116 type) was impregnated with the epoxy resin varnish obtained in Example 13 and dried at 150 ° C. for 5 minutes to produce a prepreg having a resin amount of 46% by weight. did. This prepreg was bent at 180 ° and the scattering amount of the resin powder was measured to be 1.6 mg / m.
【００７５】次にこのプリプレグを８枚重ね、両側に１
８μｍ厚の銅箔を配し、１７０℃、３０ｋｇ／ｃｍ2、
９０分間の条件で加熱加圧して積層成形して、銅張り積
層板を作製した。この銅張り積層板の銅箔をエッチング
除去して硬化樹脂を露出させて観察したところ、ボイド
やカスレなどの不良はみられず、成形性は良好であっ
た。またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭ
Ａ法で測定したところ、１７５℃であった。Next, eight prepregs were stacked, and one on each side.
A copper foil having a thickness of 8 μm is placed, and 170 ° C., 30 kg / cm 2 ,
Laminate molding was performed by heating and pressing under the conditions of 90 minutes to produce a copper-clad laminate. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. Further, the glass transition temperature (Tg) of this cured resin is set to TM
It was 175 ° C. as measured by Method A.
【００７６】（実施例１５）フェノキシ樹脂として、東
都化成社製の数平均分子量が１４４００のものを用いる
ようにした他は、実施例１３と同様にして固形分濃度を
３０重量％にしたエポキシ樹脂ワニスを調製した。Example 15 An epoxy resin having a solid concentration of 30% by weight in the same manner as in Example 13 except that a phenoxy resin having a number average molecular weight of 14400 manufactured by Toto Kasei was used. A varnish was prepared.
【００７７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１３と同様にして樹脂付き銅箔を作製
した。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の
飛散量を測定したところ、０．５ｍｇ／ｍであった。Next, a resin-coated copper foil was produced in the same manner as in Example 13 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° and the scattering amount of the resin powder was measured to be 0.5 mg / m.
【００７８】また、この樹脂付き銅箔を用いるようにし
た他は実施例１３と同様にして多層銅張り積層板を作製
した。この多層銅張り積層板の銅箔をエッチング除去し
て硬化樹脂を露出させて観察したところ、ボイドやカス
レなどの不良はみられず、成形性は良好であった。また
この硬化樹脂のガラス転移温度（Ｔｇ）をＴＭＡ法で測
定したところ、１６９℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 13 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids and blurring were observed, and the moldability was good. The glass transition temperature (Tg) of this cured resin was 169 ° C. as measured by the TMA method.
【００７９】（実施例１６）実施例１５で得たエポキシ
樹脂ワニスを用いるようにした他は実施例１４と同様に
してプリプレグを作製した。このプリプレグを１８０°
折り曲げて樹脂粉の飛散量を測定したところ、１．４ｍ
ｇ／ｍであった。(Example 16) A prepreg was prepared in the same manner as in Example 14, except that the epoxy resin varnish obtained in Example 15 was used. 180 degrees of this prepreg
When the resin powder was bent and the amount of resin powder scattered was measured, it was 1.4 m.
g / m.
【００８０】次にこのプリプレグを用いるようにした他
は実施例１４と同様にして銅張り積層板を作製した。こ
の銅張り積層板の銅箔をエッチング除去して硬化樹脂を
露出させて観察したところ、ボイドやカスレなどの不良
はみられず、成形性は良好であった。またこの硬化樹脂
のガラス転移温度（Ｔｇ）をＴＭＡ法で測定したとこ
ろ、１７２℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 14 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, no defects such as voids or blemishes were observed, and the moldability was good. The glass transition temperature (Tg) of the cured resin was 172 ° C. as measured by the TMA method.
【００８１】（実施例１７）フェノキシ樹脂（東都化成
社製：数平均分子量８３００）４０ｇをＭＥＫで希釈し
て固形分濃度を４０重量％にしたもの１００ｇを使用す
るようにした他は、実施例１３と同様にしてエポキシ樹
脂ワニスを調製した。(Example 17) Except that 40 g of a phenoxy resin (manufactured by Toto Kasei Co., Ltd., number average molecular weight: 8300) was diluted with MEK to a solid concentration of 40% by weight, and 100 g was used. In the same manner as in Example 13, an epoxy resin varnish was prepared.
【００８２】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１３と同様にして樹脂付き銅箔を作製
した。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の
飛散量を測定したところ、０．３ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 13 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 0.3 mg / m.
【００８３】また、この樹脂付き銅箔を用いるようにし
た他は実施例１３と同様にして多層銅張り積層板を作製
した。この多層銅張り積層板の銅箔をエッチング除去し
て硬化樹脂を露出させて観察したところ、ボイドやカス
レがみられた。またこの硬化樹脂のガラス転移温度（Ｔ
ｇ）をＴＭＡ法で測定したところ、１６４℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 13 except that this resin-coated copper foil was used. When the copper foil of the multilayer copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed. Also, the glass transition temperature (T
g) was 164 ° C. as measured by the TMA method.
【００８４】（実施例１８）実施例１７で得たエポキシ
樹脂ワニスを用いるようにした他は実施例１４と同様に
してプリプレグを作製した。このプリプレグを１８０°
折り曲げて樹脂粉の飛散量を測定したところ、１．０ｍ
ｇ／ｍであった。(Example 18) A prepreg was prepared in the same manner as in Example 14 except that the epoxy resin varnish obtained in Example 17 was used. 180 degrees of this prepreg
When it was bent and the scattering amount of the resin powder was measured, it was 1.0 m
g / m.
【００８５】次にこのプリプレグを用いるようにした他
は実施例１４と同様にして銅張り積層板を作製した。こ
の銅張り積層板の銅箔をエッチング除去して硬化樹脂を
露出させて観察したところ、ボイドやカスレがみられ
た。またこの硬化樹脂のガラス転移温度（Ｔｇ）をＴＭ
Ａ法で測定したところ、１６１℃であった。Next, a copper-clad laminate was produced in the same manner as in Example 14 except that this prepreg was used. When the copper foil of the copper-clad laminate was etched away to expose the cured resin and observed, voids and blurring were observed. Further, the glass transition temperature (Tg) of this cured resin is set to TM
It was 161 ° C. as measured by Method A.
【００８６】（比較例５）フェノキシ樹脂を使用せず、
固形分濃度を５０重量％にするようにした他は実施例１
３と同様にしてエポキシ樹脂ワニスを調製した。(Comparative Example 5) Without using a phenoxy resin,
Example 1 except that the solid concentration was set to 50% by weight.
In the same manner as in Example 3, an epoxy resin varnish was prepared.
【００８７】次にこのエポキシ樹脂ワニスを用いるよう
にした他は実施例１３と同様にして樹脂付き銅箔を作製
した。この樹脂付き銅箔を１８０°折り曲げて樹脂粉の
飛散量を測定したところ、３８ｍｇ／ｍであった。Next, a resin-coated copper foil was prepared in the same manner as in Example 13 except that the epoxy resin varnish was used. This resin-coated copper foil was bent at 180 ° to measure the scattering amount of the resin powder, and it was 38 mg / m.
【００８８】また、この樹脂付き銅箔を用いるようにし
た他は実施例１３と同様にして多層銅張り積層板を作製
した。この多層銅張り積層板の銅箔をエッチング除去し
て硬化樹脂を露出させて観察したところ、ボイドやカス
レなどの不良はみられなかった。またこの硬化樹脂のガ
ラス転移温度（Ｔｇ）をＴＭＡ法で測定したところ、１
７７℃であった。A multilayer copper-clad laminate was produced in the same manner as in Example 13 except that the copper foil with resin was used. When the copper foil of the multilayer copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids and blurring were found. When the glass transition temperature (Tg) of this cured resin was measured by the TMA method,
77 ° C.
【００８９】（比較例６）比較例５で得たエポキシ樹脂
ワニスを用いるようにした他は実施例１４と同様にして
プリプレグを作製した。このプリプレグを１８０°折り
曲げて樹脂粉の飛散量を測定したところ、１６０ｍｇ／
ｍであった。Comparative Example 6 A prepreg was prepared in the same manner as in Example 14 except that the epoxy resin varnish obtained in Comparative Example 5 was used. When this prepreg was bent 180 ° and the amount of resin powder scattered was measured, it was 160 mg /
m.
【００９０】次にこのプリプレグを用いるようにした他
は実施例１４と同様にして銅張り積層板を作製した。こ
の銅張り積層板の銅箔をエッチング除去して硬化樹脂を
露出させて観察したところ、ボイドやカスレなどの不良
はみられなかった。またこの硬化樹脂のガラス転移温度
（Ｔｇ）をＴＭＡ法で測定したところ、１７６℃であっ
た。Next, a copper clad laminate was produced in the same manner as in Example 14 except that this prepreg was used. When the copper foil of the copper-clad laminate was removed by etching to expose the cured resin and observed, no defects such as voids or blurring were found. The glass transition temperature (Tg) of the cured resin measured by the TMA method was 176 ° C.
【００９１】[0091]
【表３】 [Table 3]
【００９２】[0092]
【発明の効果】上記のように本発明の請求項１に係るエ
ポキシ樹脂組成物は、１分子中に３個以上のエポキシ基
を持つエポキシ樹脂と、ブタジエン−アクリロニトリル
共重合ゴムとを構成成分として含有するので、ブタジエ
ン−アクリロニトリル共重合ゴムの配合によって、樹脂
の可撓性を高めることができ、このエポキシ樹脂組成物
を用いて作製したプリプレグや樹脂付き金属箔を切断す
るにあたって、樹脂粉が飛散することを低減することが
できるものである。As described above, the epoxy resin composition according to claim 1 of the present invention comprises an epoxy resin having three or more epoxy groups in one molecule and a butadiene-acrylonitrile copolymer rubber as constituents. Since it contains, the flexibility of the resin can be enhanced by blending the butadiene-acrylonitrile copolymer rubber, and the resin powder is scattered when cutting the prepreg or the metal foil with the resin produced using this epoxy resin composition. Can be reduced.
【００９３】また本発明の請求項２に係るエポキシ樹脂
組成物は、１分子中に３個以上のエポキシ基を持つエポ
キシ樹脂と、ポリビニルアセタール樹脂とを構成成分と
して含有するので、ポリビニルアセタール樹脂の配合に
よって、樹脂の可撓性を高めることができ、このエポキ
シ樹脂組成物を用いて作製したプリプレグや樹脂付き金
属箔を切断するにあたって、樹脂粉が飛散することを低
減することができるものである。The epoxy resin composition according to claim 2 of the present invention contains, as constituents, an epoxy resin having three or more epoxy groups in one molecule and a polyvinyl acetal resin. By blending, it is possible to increase the flexibility of the resin, and it is possible to reduce scattering of resin powder when cutting a prepreg or a metal foil with a resin produced using this epoxy resin composition. .
【００９４】また本発明の請求項３に係るエポキシ樹脂
組成物は、１分子中に３個以上のエポキシ基を持つエポ
キシ樹脂と、数平均分子量７０００〜１５０００のフェ
ノキシ樹脂とを構成成分として含有するので、数平均分
子量７０００〜１５０００のフェノキシ樹脂の配合によ
って、樹脂の可撓性を高めることができ、このエポキシ
樹脂組成物を用いて作製したプリプレグや樹脂付き金属
箔を切断するにあたって、樹脂粉が飛散することを低減
することができるものである。The epoxy resin composition according to claim 3 of the present invention contains, as constituent components, an epoxy resin having three or more epoxy groups in one molecule and a phenoxy resin having a number average molecular weight of 7000 to 15000. Therefore, by blending a phenoxy resin having a number average molecular weight of 7000 to 15,000, the flexibility of the resin can be increased. When cutting a prepreg or a metal foil with a resin produced using this epoxy resin composition, the resin powder It is possible to reduce scattering.
【００９５】本発明の請求項４に係るプリプレグは、１
分子中に３個以上のエポキシ基を持つエポキシ樹脂に、
ブタジエン−アクリロニトリル共重合ゴムや、ポリビニ
ルアセタール樹脂や、数平均分子量７０００〜１５００
０のフェノキシ樹脂を配合したエポキシ樹脂組成物を基
材に含浸して作製されたものであるから、プリプレグの
半硬化状態の樹脂は可撓性が高められており、プリプレ
グを切断するにあたって樹脂粉が飛散することを低減す
ることができるものである。The prepreg according to claim 4 of the present invention has the following structure.
Epoxy resin with three or more epoxy groups in the molecule,
Butadiene-acrylonitrile copolymer rubber, polyvinyl acetal resin, number average molecular weight 7000 to 1500
Since the prepreg is prepared by impregnating a base material with an epoxy resin composition containing a phenoxy resin, the semi-cured resin of the prepreg has enhanced flexibility, and the resin powder is used for cutting the prepreg. Can be reduced.
【００９６】本発明の請求項５に係る樹脂付き金属箔
は、１分子中に３個以上のエポキシ基を持つエポキシ樹
脂に、ブタジエン−アクリロニトリル共重合ゴムや、ポ
リビニルアセタール樹脂や、数平均分子量７０００〜１
５０００のフェノキシ樹脂を配合したエポキシ樹脂組成
物を金属箔の表面に塗布して作製されたものであるか
ら、樹脂付き金属箔の半硬化状態の樹脂は可撓性が高め
られており、樹脂付き銅箔を切断するにあたって樹脂粉
が飛散することを低減することができるものである。The metal foil with resin according to claim 5 of the present invention is characterized in that an epoxy resin having three or more epoxy groups in one molecule, butadiene-acrylonitrile copolymer rubber, polyvinyl acetal resin, or a number average molecular weight of 7000 ~ 1
Since the epoxy resin composition containing 5000 phenoxy resin is applied to the surface of the metal foil, the semi-cured resin of the resin-coated metal foil has increased flexibility, It is possible to reduce scattering of the resin powder when cutting the copper foil.
【００９７】本発明の請求項６に係る積層板は、請求項
４のプリプレグと請求項５の樹脂付き金属箔の少なくと
も一方を用いて積層成形して作製されたものであるか
ら、積層板は可撓性を高めて切断時の樹脂粉の発生が低
減された半硬化樹脂からなるプリプレグや樹脂付き金属
箔によって形成されるものであり、この積層板を加工し
てプリント配線板を製造するにあたって、金属箔に樹脂
粉が付着して金属箔が残存するような問題がなくなり、
絶縁性不良やショートなどを未然に防いでプリント配線
板の信頼性を高めることができるものである。The laminate according to claim 6 of the present invention is manufactured by laminating and molding using at least one of the prepreg of claim 4 and the metal foil with resin of claim 5. It is formed of a prepreg made of semi-cured resin and a metal foil with resin, which has increased flexibility and reduced generation of resin powder at the time of cutting, and is used for manufacturing a printed wiring board by processing this laminated board. This eliminates the problem that the resin powder adheres to the metal foil and the metal foil remains,
It is possible to improve the reliability of the printed wiring board by preventing insulation failure and short circuit beforehand.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｊ 5/24 ＣＦＣ Ｃ０８Ｌ 9/02 Ｃ０８Ｌ 9/02 29/14 29/14 71/12 71/12 Ｃ０９Ｄ 109/02 Ｃ０９Ｄ 109/02 129/14 129/14 163/00 163/00 171/12 171/12 // Ｂ２９Ｋ 63:00 (72)発明者 田宮 裕記 大阪府門真市大字門真1048番地松下電工株 式会社内 (72)発明者 伊藤 克彦 大阪府門真市大字門真1048番地松下電工株 式会社内 Ｆターム(参考） 4F072 AA02 AA07 AB02 AB03 AB09 AB28 AB29 AB31 AD02 AD05 AD08 AD27 AD28 AD42 AD52 AD54 AE02 AE03 AE11 AF14 AF28 AG03 AG16 AG19 AH02 AH21 AK02 AK05 AK06 AL13──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C08J 5/24 CFC C08J 5/24 CFC C08L 9/02 C08L 9/02 29/14 29/14 71/12 71/12 C09D 109/02 C09D 109/02 129/14 129/14 163/00 163/00 171/12 171/12 // B29K 63:00 (72) Inventor Hiroki Tamiya 1048 Odakadoma, Oji, Kadoma, Osaka Matsushita Electric Works Co., Ltd. AE03 AE11 AF14 AF28 AG03 AG16 AG19 AH02 AH21 AK02 AK05 AK06 AL13
Claims (6)
エポキシ樹脂と、ブタジエン−アクリロニトリル共重合
ゴムとを構成成分として含有して成ることを特徴とする
エポキシ樹脂組成物。An epoxy resin composition comprising, as constituents, an epoxy resin having three or more epoxy groups in one molecule and a butadiene-acrylonitrile copolymer rubber.
エポキシ樹脂と、ポリビニルアセタール樹脂とを構成成
分として含有して成ることを特徴とするエポキシ樹脂組
成物。2. An epoxy resin composition comprising, as constituents, an epoxy resin having three or more epoxy groups in one molecule and a polyvinyl acetal resin.
エポキシ樹脂と、数平均分子量７０００〜１５０００の
フェノキシ樹脂とを構成成分として含有して成ることを
特徴とするエポキシ樹脂組成物。3. An epoxy resin composition comprising, as constituents, an epoxy resin having three or more epoxy groups in one molecule and a phenoxy resin having a number average molecular weight of 7000 to 15000.
シ樹脂組成物を基材に含浸して成ることを特徴とするプ
リプレグ。4. A prepreg comprising a substrate impregnated with the epoxy resin composition according to claim 1.
シ樹脂組成物を金属箔の表面に塗布して成ることを特徴
とする樹脂付き金属箔。5. A resin-coated metal foil obtained by applying the epoxy resin composition according to claim 1 to a surface of the metal foil.
付き金属箔の少なくとも一方を用いて積層成形して成る
ことを特徴とする積層板。6. A laminated plate formed by laminating at least one of the prepreg according to claim 4 and the metal foil with resin according to claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30506898A JP2000129087A (en) | 1998-10-27 | 1998-10-27 | Epoxy resin composition, prepreg, resin-coated metallic foil and laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30506898A JP2000129087A (en) | 1998-10-27 | 1998-10-27 | Epoxy resin composition, prepreg, resin-coated metallic foil and laminate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000129087A true JP2000129087A (en) | 2000-05-09 |
Family
ID=17940740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP30506898A Withdrawn JP2000129087A (en) | 1998-10-27 | 1998-10-27 | Epoxy resin composition, prepreg, resin-coated metallic foil and laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000129087A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004231788A (en) * | 2003-01-30 | 2004-08-19 | Hitachi Chem Co Ltd | Manufacturing method of insulating resin sheet and metal foil coated with insulated resin |
| KR100491754B1 (en) * | 2002-09-11 | 2005-05-27 | 주식회사 엘지화학 | Resin coated copper composition for substrate of build-up preinted circuit board |
| CN112831153A (en) * | 2020-12-31 | 2021-05-25 | 惠州市富邦电子科技有限公司 | Epoxy resin composition and prepreg and laminated board prepared from same |
-
1998
- 1998-10-27 JP JP30506898A patent/JP2000129087A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100491754B1 (en) * | 2002-09-11 | 2005-05-27 | 주식회사 엘지화학 | Resin coated copper composition for substrate of build-up preinted circuit board |
| JP2004231788A (en) * | 2003-01-30 | 2004-08-19 | Hitachi Chem Co Ltd | Manufacturing method of insulating resin sheet and metal foil coated with insulated resin |
| CN112831153A (en) * | 2020-12-31 | 2021-05-25 | 惠州市富邦电子科技有限公司 | Epoxy resin composition and prepreg and laminated board prepared from same |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A300 | Withdrawal of application because of no request for examination |
Free format text: JAPANESE INTERMEDIATE CODE: A300 Effective date: 20060110 |